- Solvent effect on the rate of the Mannich reaction of butyraldehyde with formaldehyde
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The Mannich reaction of formaldehyde with butyraldehyde and diethylamine in hydrophilic solvents ensuring homogeneity of the medium follows the kinetic relations typical of an irreversible second-order reaction. The rate constants are determined by the ability of solvents to undergo self-association and their electrophilic solvation power; additional inclusion of the solvent polarity via multiparameter Koppel'-Pal'm equation is necessary to obtain a satisfactory quantitative correlation.
- Marshalok,Karpyak,Makitra,Polyuzhin
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Read Online
- ODORANTS AND COMPOSITIONS COMPRISING ODORANTS
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The present invention relates to new classes of odorous 3-(2- methylenealkoxy)alkanenitrile derivatives of formula (I) which are useful as fragrance or flavor materials in particular in providing dry, woody, dusty, earthy, and/or patchouli notes together with optional coriander, aldehydic, citrus, mandarin, pear, cinnamon, and/ or petal floral-like notes to perfume, aroma or deodorizing/masking compositions.
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Page/Page column 24
(2021/10/22)
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- PREPARING METHOD OF DIMETHYLOLBUTANAL AND PREPERATION METHOD OF TRIMETHYLOLPROPANE USING THE SAME
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A method for preparing dimethylolbutanal according to one embodiment of the present application comprises the steps of: performing a first aldol reaction with n-butylaldehyde and a first formaldehyde under a first alkylamine catalyst to prepare a first active ingredient including dimethylol butanal and a by-product including ethyl acrolein; performing a distillation process to separate the by-product including the ethyl acrolein; and performing a second aldol reaction with the separated by-product including ethyl acrolein and a second formaldehyde under a second alkylamine catalyst to prepare a second active ingredient including dimethylol butanal.
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Paragraph 0025; 0056-0059; 0073-0079; 0082-0085; 0090
(2021/02/16)
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- Enantioselective hydroesterificative cyclization of 1,6-enynes to chiral γ-lactams bearing a quaternary carbon stereocenter
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A palladium-catalyzed asymmetric hydroesterification-cyclization of 1,6-enynes with CO and alcohol was developed to efficiently prepare a variety of enantioenriched γ-lactams bearing a chiral quaternary carbon center and a carboxylic ester group. The approach featured good to high chemo-, region-, and enantioselectivities, high atom economy, and mild reaction conditions as well as broad substrate scope. The correlation between the multiple selectivities of such process and the N-substitutes of the amide linker in the 1,6-enyne substrate has been depicted by the crystallographic evidence and control experiments.
- Dong, Kaiwu,Li, Huimin,Ren, Xinyi,Shen, Chaoren,Tang, Lin,Wang, Peng
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supporting information
p. 3561 - 3566
(2021/05/29)
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- Three Ways Aliphatic Aldehydes React with Nonstabilized Azomethine Ylides
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Aliphatic aldehydes readily react with nonstabilized azomethine ylides in one of the three ways to give oxazolidines, pyrrolidines, or Mannich bases, depending on the structure of the starting compound and the reaction conditions. The use of N -(methoxymethyl)- N -[(trimethylsilyl)methyl]benzylamine in DMF provided 5-alkyloxazolidines in 40-97percent yields. On the other hand, three-component reactions of aliphatic aldehydes bearing one α-hydrogen with N -methyl(benzyl)glycine and formaldehyde gives Mannich bases in yields of 47-98percent. A similar reaction of aldehydes bearing branched alkyl groups and two hydrogen atoms at the α-position proceeds as a domino process that gives 3-alkyl-3-formylpyrrolidines in yields of 34-93percent.
- Buev, Evgeny M.,Gorbunova, Evgeniya V.,Moshkin, Vladimir S.,Sosnovskikh, Vyacheslav Y.
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supporting information
p. 343 - 348
(2020/02/27)
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- Synthetic method of 2-ethylacrylaldehyde
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The invention discloses a synthetic method of 2-ethylacrylaldehyde and belongs to the technical field of organic synthesis. According to the method, n-butanal and formaldehyde are subjected to a reaction for 2-4 h at 40-60 DEG C under catalysis of a di-n-butylamine and B(C6F5)3 mixed system, a reaction liquid is left to stand for layering, an organic layer is taken, 0.1%-0.5% of a polymerization inhibitor is added, a mixture is distilled under normal pressure, a colorless transparent product 2-ethylacrylaldehyde is obtained, and 0.1%-0.5% of the polymerization inhibitor is added for storage. The route is simple to operate, few by-products are produced in the reaction, and the product is high in purity, is not prone to polymerization and has competitive advantage.
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Paragraph 0013-0020
(2019/01/14)
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- The bioinspired design of a reagent allows the functionalization of Cα-H of α,β-unsaturated carbonyl compounds via the Baylis-Hillman chemistry under ambient conditions
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A rationally designed reagent capable of affecting alkylation at Cα of α,β-unsaturated carbonyl compounds is reported. The reaction proceeded at room temperature without any additives. The pH and H-bond formation during the reaction play a key role in the working of the reagent.
- Singh, Palwinder,Kumar, Arun,Kaur, Sukhmeet,Kaur, Jagroop,Singh, Harpreet
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supporting information
p. 2936 - 2939
(2016/02/20)
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- Catalytic Asymmetric Synthesis of Isoxazolines from Silyl Nitronates
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1,3-Dipolar cycloadditions of triisopropylsilyl nitronates and 2-alkylacroleins produced isoxazolines bearing a chiral quaternary center in high yields and enantioselectivities with the aid of a chiral oxazaborolidine catalyst. One chiral isoxazoline product was converted to (R)-(+)-Tanikolide in 9 steps in a total yield of 43%. (Chemical Equation Presented).
- Han, Xiaoyu,Dong, Li,Geng, Caiwei,Jiao, Peng
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supporting information
p. 3194 - 3197
(2015/07/15)
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- Lewis Acid Catalyzed Formal Intramolecular [3 + 3] Cross-Cycloaddition of Cyclopropane 1,1-Diesters for Construction of Benzobicyclo[2.2.2]octane Skeletons
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A novel Lewis acid catalyzed formal intramolecular [3 + 3] cross-cycloaddition (IMCC) of cyclopropane 1,1-diesters has been successfully developed. This supplies an efficient and conceptually new strategy for construction of bridged bicyclo[2.2.2]octane skeletons. This [3 + 3]IMCC could be run up to gram scale and from easily prepared starting materials. This [3 + 3]IMCC, together with our previously reported [3 + 2]IMCC strategy, can afford either the bicyclo[2.2.2]octane or bicyclo[3.2.1]octane skeletons from the similar starting materials by regulating the substituents on vinyl group.
- Ma, Weiwei,Fang, Jie,Ren, Jun,Wang, Zhongwen
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supporting information
p. 4180 - 4183
(2015/09/15)
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- PROCESS FOR PRODUCTION OF DITRIMETHYLOLPROPANE
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Provided is a method for producing di-TMP by reacting n-butyl aldehyde (NBD), formaldehyde and a base, said method including a first step of reacting the NBD, formaldehyde (1) and a base (I) to obtain a reaction mixture solution containing trimethylolpropane (TMP), di-TMP and 2-ethyl-2-propenal (ECR); a second step of distilling the reaction mixture solution to recover the ECR therefrom; and a third step of sequentially adding the ECR recovered by distillation, and adding at least one of a base (II) and formaldehyde (2), to the reaction mixture solution from which the ECR has been recovered by distillation, and thereby allowing a reaction for production of the di-TMP to proceed gradually, in which TMP is added in any one of the first to third steps or in plural steps of the first to third steps.
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Paragraph 0102
(2014/05/20)
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- METHOD FOR PRODUCING DITRIMETHYLOLPROPANE
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The present invention provides a method for producing ditrimethylolpropane which is characterized by the following (1) and (2): (1) a distillation still residue separated from purified trimethylolpropane is subjected to re-distillation under specific conditions to obtain a ditrimethylolpropane-containing solution having given contents of bis-TMP and tri-TMP; and (2) when subjecting the ditrimethylolpropane-containing solution to crystallization with an organic solvent, the crystallization is initiated under pressure at a temperature exceeding a boiling point of the organic solvent as measured under normal pressures, and the resulting crystallization product solution is cooled at a temperature drop rate of 2° C./min or less. According to the above method, it is possible to produce a high-purity ditrimethylolpropane from a distillation still residue obtained upon production of trimethylolpropane in a simple, industrially useful manner.
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Paragraph 0143; 0144; 0145
(2013/07/25)
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- Enantioselective allylation of α,β-unsaturated aldehydes with allyltrichlorosilane catalyzed by METHOX
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α,β-Unsaturated aldehydes 6a-j undergo an enantioselective allylation with allylic trichlorosilanes 2a,b in the presence of METHOX (4) as a Lewis basic catalyst (≤10 mol %) to produce the homoallylic alcohols 7a-l at good to high enantioselectivity (83-96% ee). This study shows that the reactivity scope of METHOX can be extended from aromatic to nonaromatic aldehydes.
- Malkov, Andrei V.,Barlog, MacIej,Jewkes, Yvonne,Mikusek, Jiri,Kocovsky, Pavel
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body text
p. 4800 - 4804
(2011/07/09)
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- Cooperative copper(I) and primary amine catalyzed room-temperature carbocyclization of formyl alkynes
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An efficient CuI/amine catalytic system is described for the carbocyclization of α-disubstituted formylalkynes at room temperature. Merging aminocatalysis to the copper(I)-catalyzed activation of alkynes led to clean carbocyclization of a wide range of functionalized substrates under mild conditions. This novel cooperative catalytic system allowed the formation of a variety of carbo- and heterocycles, including pyrrolidines, in good to excellent yields. Mechanistic aspects of this process are also discussed. Copyright
- Montaignac, Benjamin,Vitale, Maxime R.,Ratovelomanana-Vidal, Virginie,Michelet, Veronique
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supporting information; scheme or table
p. 3723 - 3727
(2011/09/12)
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- PROCESS FOR PRODUCTION OF DITRIMETHYLOLPROPANE
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The present invention provides a method for producing ditrimethylolpropane including reacting n-butyraldehyde with formaldehyde in the presence of a base catalyst to thereby produce trimethylolpropane and ditrimethylolpropane, wherein the method includes (I) a step of reacting n-butyraldehyde with formaldehyde (1) in the presence of a base catalyst (1), to thereby produce a reaction mixture containing trimethylolpropane, ditrimethylolpropane, and 2-ethyl-2-propenal; (II) a step of recovering 2-ethyl-2-propenal through distillation of the produced reaction mixture; and (III) a step of adding, to a distillation residue obtained through recovery of 2-ethyl-2-propenal, the recovered 2-ethyl-2-propenal and formaldehyde (2), and optionally a base catalyst (2), to thereby allow reaction for production of ditrimethylolpropane to proceed, wherein the amounts of formaldehyde (I) and the base catalyst (1) supplied in step I and formaldehyde (2) and the base catalyst (2) supplied in step II are controlled to specific amounts, to thereby effectively produce ditrimethylolpropane. According to the present invention, the yield of di-TMP is considerably increased, and the amount of bis-TMP by-produced can be considerably reduced with respect to the amount of di-TMP (i.e., a product of interest) produced; that is, di-TMP can be effectively produced in an industrially advantageous manner.
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Page/Page column 9
(2010/07/10)
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- Organocatalyzed cyclopropanation of α-substituted α,β-unsaturated aldehydes: Enantioselective synthesis of cyclopropanes bearing a chiral quaternary center
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An enantioselective cyclopropanation of α-substituted α,β-unsaturated aldehydes with bromomalonate has been successfully developed through a domino Michael/a-alkylation strategy. The method allows the efficient formation of cyclopropanes bearing a quaternary carbon stereocenter at the a-position of the aldehydes by using iminium/enamine catalysis and gives a nice extension on the organocatalytic cyclopropanation of bromomalonate and α β-unsaturated aldehydes previously reported by other groups. Very good yields (up to 81%) and enantioselectivities (up to 97% ee) have been obtained. The optically active cyclopropane derivatives are of high synthetic interest as useful targets for further elaboration into more complex structures. 2010 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim aldehydes, cyclopropanes, domino reactions, organocatalysis, quaternary stereocenters.
- Terrasson, Vincent,Van Der Lee, Arie,De Figueiredo, Renata Mareia,Campagne, Jean Marc
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supporting information; experimental part
p. 7875 - 7880
(2010/09/18)
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- Process for producing alpha,alpha-bis (hydroxymethyl )alkanal
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The present invention provides a process for producing an α,α-bis(hydroxymethyl)alkanal represented by Formula (II): (wherein R represents an alkyl group, a cycloalkyl group, or an aryl group) which comprises reacting an aldehyde represented by Formula (I): [in-line-formulae]R—CH2—CHO??(I) [/in-line-formulae] (wherein R has the same meaning as defined above) with formaldehyde in the presence of a basic catalyst and a phase-transfer catalyst.
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Page/Page column 3-4
(2008/06/13)
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- Process for producing 2,2'-bis-(hydroxymethyl)alkanal and 2,2'-bis(hydroxymethyl)alkanoic acid
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The present invention relates to a process for producing 2,2'-bis(hydroxymethyl)alkanal and 2,2'-bis(hydroxymethyl)alkanoic acid as raw materials for dimethylol alkanoic acids or trimethylol alkanes, which are useful for the production of polyesters, polyurethanes, alkyd resins and the like, in an industrially advantageous manner.
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Page column 12-16
(2008/06/13)
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- Comparison of activity and selectivity of weakly basic anion-exchange catalysts for the aldolization of butyraldehyde with formaldehyde
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Aldols are important intermediates in the production of polyols, which are raw material for lubricants, surface coatings, and synthetic resins. The activities and selectivities of gel-type and macroporous anion-exchange resin catalysts in the aldolization of butyraldehyde with formaldehyde in an aqueous environment were investigated at 60 °C. The experiments were carried out batchwise in a stirred glass reactor, and the reaction products were analyzed with high performance liquid chromatography. Two main products were observed, 2-ethyl-3-hydroxy-2-hydroxy-methylpropanal (trimethylolpropane aldol) and 2-ethyl-propenal (ethylacrolein). The product ratio was strongly dependent on the catalyst. The selectivity with respect to trimethylolpropane aldol varied within the range 2.7-7.3 for the catalysts investigated. Systematic kinetic experiments were carried out at 50-70 °C with the gel-type resin catalyst displaying the highest aldol selectivity. A kinetic model based on molecular mechanisms was able to describe the product distribution.
- Serra-Holm,Salmi,Maeki-Arvela,Paatero,Lindfors
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p. 368 - 375
(2013/09/07)
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- Contrast media synthesized from polyaldehydes
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Microparticles comprising biodegradable polymers, characterized in that they are synthesized from polymerizable aldehydes, which optionally contain additives and/or crosslinkers capable of copolymerization, optionally surfactants or surfactant mixtures, gases and/or highly volatile liquids in free or bound form, coupling agents, optionally biomolecules or macromolecules bound by these coupling agents as well as optionally diagnostically or therapeutically effective components, are suitable as ultrasonic contrast media.
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- SYNTHESIS AND REACTIONS OF SUBSTITUTED ACROLEINS.
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In this work we examined methods for obtaining 2-alkylacroleins and their derivatives that would render these compounds as cheap and readily available products of organic synthesis. Using aldehydes we show that ethylene glycol, glycerin, and pentaerythritol in the presence of acid catalysts react primarily at the carbonyl group. Maximal yields (50-80%) were obtained when using the cation exchanger KU-2 as the acid catalyst, which also simplified the isolation of the desired products. The 2-alkyl-1,3-dioxacyclanes obtained are of particular interest as monomers, comonomers, and intermediate products of organic synthesis.
- Saprygina,Zlot-skii,Rakhmankulov
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p. 862 - 866
(2007/10/02)
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- BIOSYNTHESIS OF β-METHYLENENORVALINE (2-AMINO-3-ETHYL-3-BUTENOIC ACID) IN PHILADELPHUS
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Key Word Index - Philadelphus; Saxifragaceae; β-methylenenorvaline; 2-amino-3-ethyl-3-butenoic acid; biosynthesis; synthesis. β-Methylenenorvaline (2-amino-3-ethyl-3-butenoic acid) was synthesized.The specific incorporation of isoleucine (as a mixture of L-isoleucine and D-alloisoleucine) into β-methylenenorvaline in Philadelphus cv Belle Etoile was demonstrated.
- Crout, David H. G.,Piper, Ian M.,Sehgal, Charanjit K.
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p. 1399 - 1402
(2007/10/02)
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- Preparation of alpha-alkylacroleins
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α-Alkylacroleins are prepared by reacting an alkanal with formaldehyde and a secondary amine in the presence of a carboxylic, dicarboxylic or polycarboxylic acid in certain molar ratios within a pH range of from 2.5 to 7 and at from 0° to 150° C. The α-alkylacroleins which can be prepared by the process described are valuable starting materials for dyes, drugs and pest control agents.
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